Oxidative Degradation of 4-chlorophenol in Aqueous Induced by Plasma with Submersed Glow Discharge Electrolysis

The oxidative degradation of 4-chlorophenol （4-CP） in aqueous solution induced by plasma with submersed glow discharge has been investigated. The concentration of 4-CP and the reaction intermediates were determined by high performance liquid chromatography （HPLC）. Various influencing factors such as the initial pH, the concentration of 4-CP and the catalytic action of Fe^2＋ were examined. The results indicate that 4-CP is eventually degraded into inorganic ion, dioxide carbon and water. The attack of hydroxyl radicals on the benzene rings of 4-CP in the initial stage of oxidative reactions is presumed to be a key step. They also suggest that the reaction is of a pseudo-first order kinetic reaction and the proposed method is an efficient way for the 4-CP degradation,     

Atmospheric Pressure Plasma Jet in Organic Solution: Spectra,Degradation Effects of Solution Flow Rate and Initial pH Value

The organic compounds of p-nitrophenol （PNP） solution was treated by the active species generated in a stirred reactor by an atmospheric pressure plasma jet （APPJ）. The emission intensities of hydroxyl （OH）, oxygen （O）, nitric oxide （NO）, hydrogen （H） and molecular （N2） were measured by optical emission spectroscopy （OES）. The relations between the flow rates of the PNP solution and degradation, the degradation effects and initial pH value of the solution were also investigated. Experimental results show that there exist intense emissions of O （777.1 nm）, N（337.1 nm）, OH （306-310 nm） and NO band （200-290 nm） in the region of plasma. Given the treatment time and gas flow rate, the degradation increased as a function of discharge energy and solution flow rate, respectively. The solution flow rate for the most efficient degradation ranged from 1.414 m/s to 1.702 m/s, and contributed very little when it exceeded 2.199 m/s. This indicates the existence of diffusion-controlled reactions at a low solution flow rate and activation- controlled reactions at a high solution flow rate. Moreover, increasing or decreasing the initial pH value of neutral PNP solution （pH=5.95） could improve the degradation efficiency. Treated by APPJ, the PNP solutions with different initial pH values of 5.95, 7.47 and 2.78 turned more acidic in the end, while the neutral solution had the lowest degradation efficiency. This work clearly demonstrates the close coupling of active species, photolysis of ultraviolet, the organic solution flow rate and the initial pH value, and thus is helpful in the study of the mechanism and application of plasma in wastewater treatment.     

Research on quinoline degradation in drinking water by a large volume strong ionization dielectric barrier discharge reaction system

Quinoline is widely used in the production of drugs as a highly effective insecticide, and its derivatives can also be used to produce dyes. It has a teratogenic carcinogen to wildlife and humans once entering into the aquatic environment. In this study, the degradation mechanism of quinoline in drinking water by a strong ionization dielectric barrier discharge(DBD) lowtemperature plasma with large volume was explored. High concentration of hydroxyl radical(·OH)(0.74 mmol l-1) and ozone(O3)(58.2 mg l-1) produced by strongly ionized discharge DBD system were quantitatively analyzed based on the results of electron spin resonance and O3 measurements. The influencing reaction conditions of input voltages, initial p H value, ·OH inhibitors, initial concentration and inorganic ions on the removal efficiency of quinoline were systematically studied. The obtained results showed that the removal efficiency and TOC removal of quinoline achieved 94.8% and 32.2%, degradation kinetic constant was 0.050 min-1 at 3.8 k V and in a neutral p H(7.2). The proposed pathways of quinoline were suggested based on identified intermediates as hydroxy pyridine, fumaric acid, oxalic acid, and other small molecular acids by high-performance liquid chromatography/tandem mass spectrometry analysis. Moreover, the toxicity analysis on the intermediates demonstrated that its acute toxicity, bioaccumulation factor and mutagenicity were reduced. The overall findings provided theoretical and experimental basis for the application of a high capacity strong ionization DBD water treatment system in the removal of quinoline from drinking water.     

Degradation of Anionic Dye Eosin by Glow Discharge Electrolysis Plasma

This paper describes a novel method for the degradation of eosin by using glow discharge electrolysis （GDE）. The effects of various parameters on the removal efficiency were studied. It was found that the eosin degradation could be raised considerably by increasing the applied voltage and the initial concentration, or by decreasing pH of the aqueous solution. Fe^2＋ ion had an evident accelerating effect on the eosin degradation. The degradation process of eosin obeyed a pseudo-first-order reaction. The relationship between the degradation rate constant k and the reaction temperature T could be expressed by Arrhenius equation with which the apparent activation energy Ea of 14.110 kJ· mol^-1 and the pre-exponential factor k0 of 2.065× 10^-1 min^-1 were obtained, too. The determination of hydroxyl radical was carried out by using N, N-dimethyl -p-nitrosoaniline （RNO） as a scavenger. The results showed that the hydroxyl radical plays an important role in the degradation process.     

Evaluation of influence of cold atmospheric pressure argon plasma operating parameters on degradation of aqueous solution of Reactive Blue 198(RB-198)

The intention of this work is to remove Reactive Blue 198(RB-198) dye components from simulated water solution using cold atmospheric pressure argon plasma jet. Aqueous solutions of RB-198 dye were treated as a function of various operating parameters such as applied potential,reaction time and distance between the plasma jet and surface of the liquid. The efficiency of the degradation of RB-198 molecules was explored by means of UV-Vis spectroscopy. The reactive species involved during the treatment process were examined by optical emission spectra(OES).The present hydroxyl radicals(OH·radical) and hydrogen peroxide(H_2O_2) in the plasma-treated aqueous dye solutions were investigated using various spectroscopic techniques. The other parameters such as total organic carbon(TOC), conductivity and p H were also reviewed. The toxicity of plasma-treated RB-198 solution was finally studied by diffusion bacterial analysis and by tracking seed germination processes. The results show that a higher degradation percentage of99.27% was acquired for the RB-198 treated at higher reaction time and applied potential, and shorter distance between the plasma jet and water surface. This may be due to the formation of various reactive oxygen(OH·radical, atomic oxygen(O) and H_2O_2) and nitrogen species(nitric oxide(NO) radicals and N_2 second positive system(N_2 SPS)) during the processes as confirmed by OES analysis and other spectroscopy analysis. TOC(17.7%-81.8%) and pH(7.5-3.4)values of the plasma-treated RB-198 decreased significantly with respect to various operation parameters, which indicates the decomposition of RB-198 molecules in the aqueous solution.Moreover, the conductivity of plasma-treated RB-198 aqueous solutions was found to have increased linearly during the plasma treatment due to the formation of various ionic species in aqueous solution. The toxicity analysis clearly exhibits the non-toxic behavior of plasma-treated RB-198 aqueous solution towards the bacterial growth and germination of seeds.     

Degradation of Microcystin-LR by Gas-Liquid Interfacial Discharge Plasma

In this study, we report on the degradation of microcystin-LR （MC-LR） by gas- liquid interracial discharge plasma. The influences of operation parameters such as average input voltage, electrode distance and gas flow rate are investigated. Experimental results indicate that the input voltage and gas flow rate have positive influences on MC-LR degradation, while the electrode distance has a negative one. After 6 min discharge with 25 kV average input voltage and 60 L/h air aerati by discharge both in on, the degradation rate of MC-LR achieves 75.3%. distilled water and MC-LR solution are measured H202 and 03 generated Moreover, an emission spectroscopy is used as an indicator of the processes that take place on the gas-liquid boundary and inside plasma. Varied types of radicals （O, .OH, CO, 03, etc.） are proved to be present in the gas phase during gas-liquid interfacial discharge.     

Research on the degradation mechanism of dimethyl phthalate in drinking water by strong ionization discharge

The degradation mechanism of dimethyl phthalate(DMP) in the drinking water was investigated using strong ionization discharge technology in this study. Under the optimized condition, the degradation efficiency of DMP in drinking water was up to 93% in 60 min. A series of analytical techniques including high-performance liquid chromatography, liquid chromatography mass spectrometry, total organic carbon analyzer and ultraviolet–visible spectroscopy were used in the study. It was found that a high concentration of ozone(O_3) produced by dielectric barrier discharge reactor was up to 74.4 mg l~(-1) within 60 min. Tert-butanol, isopropyl alcohol,carbonate ions(CO_3~(2-)) and bicarbonate ions (HCO_3~-) was added to the sample solution to indirectly prove the presence and effect of hydroxyl radicals(·OH). These analytical findings indicate that mono-methyl phthalate, phthalic acid(PA) and methyl ester PA were detected as the major intermediates in the process of DMP degradation. Finally, DMP and all products were mineralized into carbon dioxide(CO_2) and water(H_2O) ultimately. Based on these analysis results, the degradation pathway of DMP by strong ionization discharge technology were proposed.     

Three modes of a direct-current plasma jet operated underwater to degrade methylene blue

A direct-current air plasma jet operated underwater presents three stable modes including an intermittently-pulsed discharge, a periodically-pulsed discharge and a continuous discharge with increasing the power voltage. The three discharge modes have different appearances for the plasma plumes. Moreover, gap voltage-current characteristics indicate that the continuous discharge is in a normal glow regime. Spectral lines from reactive species(OH, N_2, N_2~+, H_α,and O) have been revealed in the emission spectrum of the plasma jet operated underwater.Spectral intensities emitted from OH radical and oxygen atom increase with increasing the power voltage or the gas flow rate, indicating that reactive species are abundant. These reactive species cause the degradation of the methylene blue dye in solution. Effects of the experimental parameters such as the power voltage, the gas flow rate and the treatment time are investigated on the degradation efficiency. Results indicate that the degradation efficiency increases with increasing the power voltage, the gas flow rate or the treatment time. Compared with degradation in the intermittently-pulsed mode or the periodically-pulsed one, it is more efficient in the continuous mode, reaching 98% after 21 min treatment.     

Evaluation of trans-ferulic acid degradation by dielectric barrier discharge plasma combined with ozone in wastewater with different water quality conditions

In this study, dielectric barrier discharge plasma and ozone(O_3) were combined to synergistically degrade trans-ferulic acid(FA), and the effect of water quality on FA degradation was studied. The results showed that 96.9% of FA was degraded after 40 min treatment by the plasma/O_3 process. FA degradation efficiency increased with the p H values. The presence of suspended solid and humic acid inhibited FA degradation. FA degradation efficiency increased as the water temperature increased to 30 °C. However, the further increase in water temperature was adverse for FA degradation. Effects of common inorganic ions on FA degradation were also investigated. The addition of Cl~- inhibited the FA degradation, whileCO_3~(2-) had both negative and positive influences on FA degradation.NO_3~- andSO_4~(2-) did not have significant effect on FA degradation. Fe~(3+)and Cu~(2+)benefited FA degradation through the Fenton-like and catalytic ozonation reactions.     

Degradation of phenol using a combination of granular activated carbon adsorption and bipolar pulse dielectric barrier discharge plasma regeneration

A combined method of granular activated carbon (GAC) adsorption and bipolar pulse dielectric barrier discharge (DBD) plasma regeneration was employed to degrade phenol in water. After being saturated with phenol, the GAC was filled into the DBD reactor driven by bipolar pulse power for regeneration under various operating parameters. The results showed that different peak voltages, air flow rates, and GAC content can affect phenol decomposition and its major degradation intermediates, such as catechol, hydroquinone, and benzoquinone. The higher voltage and air support were conducive to the removal of phenol, and the proper water moisture of the GAC was 20％. The amount of H2O2 on the GAC was quantitatively determined, and its laws of production were similar to phenol elimination. Under the optimized conditions, the elimination of phenol on the GAC was confirmed by Fourier transform infrared spectroscopy,and the total removal of organic carbons achieved 50.4％. Also, a possible degradation mechanism was proposed based on the HPLC analysis. Meanwhile, the regeneration efficiency of the GAC was improved with the discharge treatment time, which attained 88.5％ after 100 min of DBD processing.     

Hybrid electric discharge plasma technologies for water decontamination: a short review

Electric discharge plasma (EDP) can efficiently degrade aqueous pollutants by its in situ generated strong oxidative species (·OH, ·O, H₂O₂, O₃, etc) and other physiochemical effects (UV irradiation, shockwaves, local high temperature, etc), but a high energy consumptions limit the application of EDP in water treatment. Some adsorbents, catalysts, and oxidants have been employed for enhancing the degradation of pollutants by discharge plasma. These hybrid plasma technologies offer improved water treatment performance compared to discharge plasma alone. This paper reviews the water decontamination performance and mechanisms of these hybrid plasma technologies, and some suggestions on future water treatment technologies based on discharge plasma are also proposed.     

Evaluation on a double-chamber gas-liquid phase discharge reactor for benzene degradation

A double-chamber gas-liquid phase DBD reactor (GLDR), consisting of a gas-phase discharge chamber and a gas-liquid discharge chamber in series, was designed to enhance the degradation of benzene and the emission of NOx. The performance of the GLDR on discharge characteristics, reactive species production and benzene degradation was compared to that of the single-chamber gas phase DBD reactor (GPDR). The effects of discharge gap, applied voltage, initial benzene concentration, gas flow rate and solution conductivity on the degradation and energy yield of benzene in the GLDR were investigated. The GLDR presents a higher discharge power, higher benzene degradation and higher energy yield than that of the GPDR. NO₂ emission was remarkably inhibited in the GLDR, possibly due to the dissolution of NO₂ in water. The benzene degradation efficiency increased with the applied voltage, but decreased with the initial concentration, gas flow rate, and gas discharge gap, while the solution conductivity presented less influence on benzene degradation. The benzene degradation efficiency and the energy yield reached 61.11% and 1.45 g kWh^–1 at 4 mm total gas discharge gap, 15 kV applied voltage, 200 ppm benzene concentration, 0.2 L min⁻¹ gas flow rate and 721 μS cm⁻¹ water conductivity. The intermediates and byproducts during benzene degradation were detected by FT-IR, GC-MS and LC-MS primarily, and phenols, CO_x, and other aromatic substitutes, O₃, NO_x, etc, were determined as the main intermediates. According to these detected byproducts, a possible benzene degradation mechanism was proposed.     

氨基羟基脲脉冲辐解研究

研究了脉冲辐解过程中氨基羟基脲与水辐解活性粒子（e^-_aq、·OH和·H）及单电子氧化剂·CO₃^-的反应动力学过程。反应近似为准一级反应,反应速率常数分别为k（e^-aq）=1.41×10⁸ L/(mol·s)、k（·OH）=1.05×10¹⁰ L/(mol·s)、k（·H）=2.68×10⁵ L/(mol·s)、k（·CO^-₃）=4.25×10⁸ L/(mol·s)。其中氨基羟基脲与·OH的反应速率常数最大,故在辐解过程中其为主要反应。     

The effect of gas additives on reactive species and bacterial inactivation by a helium plasma jet

In this paper,the influences of gas doping(O_2,N_2,Air)on the concentrations of reactive species and bactericidal effects induced by a He plasma jet are studied.Firstly,results show that gas doping causes an increase in voltage and a decrease in current compared with the pure He discharge under the same discharge power,which might be attributed to the different chemical characteristics of O_2 and N_2 and verified by the changes in the gaseous reactive species shown in the optical emission spectroscopy(OES) and Fourier transform infrared(FTIR)spectroscopy.Secondly,the concentrations of aqueous reactive oxygen species(ROS) and reactive nitrogen species(RNS) are tightly related to the addition of O_2 and N_2 into the working gas.The concentrations of aqueous NO_2~- and NO_3~- significantly increase while the concentrations of aqueous ROS decrease with the admixture of N_2.The addition of O_2 has little effect on the concentrations of NO_2~- and NO_3~- and pH values; however,the addition of O_2 increases the concentration of O_2~- and deceases the concentrations of H_2O_2 and OH.Finally,the results of bactericidal experiments demonstrate that the inactivation efficiency of the four types of plasma jets is He?+?O_2??He+AirHeHe+N_2,which is in accordance with the changing trend of the concentration of aqueous O_2~-.Simultaneously to the better understanding of the formation and removal mechanisms of reactive species in the plasma–liquid interaction,these results also prove the effectiveness of regulating the concentrations of aqueous reactive species and the bacteria inactivation effects by gas doping.     

Plasma-catalytic degradation of tetracycline hydrochloride over Mn/γ-Al2O3 catalysts in a dielectric barrier discharge reactor

A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series ofMn/γ-Al₂O₃ catalysts prepared by the incipient wetness impregnation method. The combination of plasma and theMn/γ-Al₂O₃ catalysts significantly enhanced the degradation efficiency of tetracycline hydrochloride compared to the plasma process alone, with the 10%Mn/γ-Al₂O₃ catalyst exhibiting the best tetracycline hydrochloride degradation efficiency. A maximum degradation efficiency of 99.3% can be achieved after 5 min oxidation and a discharge power of 1.3 W, with only 69.7% by a single plasma process. The highest energy yield of the plasma-catalytic process is 91.7 gkWh⁻¹. Probable reaction mechanisms of the plasma-catalytic removal of tetracycline hydrochloride were also proposed.     

Effect of N_2 and O_2 on OH radical production in an atmospheric helium microwave plasma jet

UV-pulsed laser cavity ringdown spectroscopy of the hydroxyl radical OH(A–X)(0–0)band in the wavelength range of 306–310 nm was employed to determine absolute number densities of OH in the atmospheric helium plasma jets generated by a 2.45 GHz microwave plasma source.The effect of the addition of molecular gases N_2 and O_2 to He plasma jets on OH generation was studied.Optical emission spectroscopy was simultaneously employed to monitor reactive plasma species.Stark broadening of the hydrogen Balmer emission line(H_β)was used to estimate the electron density nein the jets.For both He/N_2 and He/O_2 jets, newas estimated to be on the order of 10~(15)cm~(-3).The effects of plasma power and gas flow rate were also studied.With increase in N_2 and O_2 flow rates, netended to decrease.Gas temperature in the He/O_2 plasma jets was elevated compared to the temperatures in the pure He and He/N_2 plasma jets.The highest OH densities in the He/N_2 and He/O_2 plasma jets were determined to be 1.0?×10~(16)molecules/cm~3 at x?=?4 mm(from the jet orifice)and 1.8?×?10~(16)molecules/cm~3 at x=3 mm, respectively.Electron impact dissociation of water and water ion dissociative recombination were the dominant reaction pathways, respectively, for OH formation within the jet column and in the downstream and far downstream regions.The presence of strong emissions of the N_2~+ bands in both He/N_2 and He/O_2 plasma jets, as against the absence of the N_2~+ emissions in the Ar plasma jets, suggests that the Penning ionization process is a key reaction channel leading to the formation of N_2~+ in these He plasma jets.     

Influence of gas atmosphere on synergistic control of mercury and dioxin by nonthermal plasma

In this paper, narrow-pulse power discharge is used to study the synergistic control of mercury and dioxins, in which 1,2,4-trichlorobenzene (TCB) was used as a dioxin analog, by using a self- designed experimental system. The competitive effects of NO, SO₂ and HCl on the TCB removal by non-thermal plasma are discussed. The influence of acid gas on TCB degradation is reflected in the competitive effect. NO has the greatest influence on TCB degradation efficiency. The oxidation efficiency of Hg⁰ decreased by about 10% in all three acidic gas atmospheres, and the effect of each gas component on Hg⁰ oxidation is complex. In the flue gas atmosphere of ‘acid gas+Hg⁰ +TCB’, the mechanism of the synergistic control of Hg⁰ and TCB by the non- thermal plasma is different, which has competition and promotion relationship between each other. The contribution of various flue gas components to the results was complicated, but the overall experimental results show that the synergistic control effect of the system can continue to improve. According to the generated product backstepping, ·OH plays an important role in the synergistic control of the degradation of Hg⁰ and TCB. Through this study, we hope to provide basic research data for the collaborative control of flue gas in the incineration industry.     

Discharge characteristics and reactive species production of unipolar and bipolar nanosecond pulsed gas–liquid discharge generated in atmospheric N_2

In this paper,unipolar pulse (including positive pulse and negative pulse) and bipolar pulse voltage are employed to generate diffuse gas–liquid discharge in atmospheric N_2with a rumpetshaped quartz tube.The current–voltage waveforms,optical emission spectra of excited state active species,FTIR spectra of exhaust gas components,plasma gas temperature,and aqueous H_2O_2,NO_2~-,andNO_3~-production are compared in three pulse modes,meanwhile,the effects of pulse peak voltage and gas flow rate on the production of reactive species are studied.The results show that two obvious discharges occur in each voltage pulse in unipolar pulse driven discharge,differently,in bipolar pulse driven discharge,only one main discharge appears in a single voltage pulse time.The intensities of active species (OH(A),and O(3p)) in all three pulsed discharge increase with the rise of pulse peak voltage and have the highest value at 200 ml min~(-1)of gas flow rate.The absorbance intensities of NO_2and N_2O increase with the increase of pulse peak voltage and decrease with the increase of gas flow rate.Under the same discharge conditions,the bipolar pulse driven discharge shows lower breakdown voltage,and higher intensities of excited species (N_2(C),OH(A),and O(3p)),nitrogen oxides (NO_2,NO,and N_2O),and higher production of aqueous H_2O_2,NO_2~-,andNO_3~-compared with both unipolar positive and negative discharges.     

In situ quantification of NO synthesis in a warm air glow discharge by WMS-based Mid-IR QCL absorption spectroscopy

Nitric oxide (NO) is one of the most crucial products in the plasma-based nitrogen fixation process. In this work, in situ measurements were performed for quantifying the NO synthesis spatially in a warm air glow discharge, through the method of Mid-infrared quantum cascade laser absorption spectroscopy (QCL-AS). Two ro-vibrational transitions at 1900.076 cm⁻¹ and 1900.517 cm⁻¹ of the ground-state NO(X) were probed sensitively by the help of the wavelength modulation spectroscopy (WMS) approach to increase the signal/noise (S/N) level. The results show a decline trend of NO synthesis rate along the discharge channel from the cathode to the anode. However, from the point of energy efficiency, the cathode region is of significantly low energy efficiency of NO production. Severe disproportionality was found for the high energy consumption but low NO production in the region of cathode area, compared to that in the positive column zone. Further analysis demonstrates the high energy cost of NO production in the cathode region, is ascribed to the extremely high reduced electric field $E/N$ therein not selectively preferable for the processes of vibrational excitation or dissociation of N₂ and O₂ molecules. This drags down the overall energy efficiency of NO synthesis by this typical warm air glow discharge, particularly for the ones with short electrode gaps. Limitations of further improving the energy cost of NO synthesis by variations of the discharge operation conditions, such as discharge current or airflow rate, imply other effective manners able to tune the energy delivery selectively to the NO formation process, are sorely needed.